Six homodinuclear and two heteronuclear complexes TpNpCo–C2O4–CoTpNp (1), TpNpCo–C2O4–NiTpCy (2), TpCyNi–C2O4–NiTpCy (3), TpNpCo–C2O2(NH)2–CoTpNp (4), TpCyNi–C2O2(NH)2–NiTpCy (5), TpNpCo–C2S2(NH)2–CoTpNp (6), TpNpCo–C2S2(NH)2–NiTpCy (7), TpCyNi–C2S2(NH)2–NiTpCy (8) (TpNp = tris(3-neopentylpyrazolyl)borate, TpCy = tris(3-cyclohexylpyrazolyl)borate), were synthesized and characterized by mass spectrometry, electronic spectroscopy and X-ray crystallography. These compounds possess similar molecular structures, with the metal ions linked by bridging oxalate (1–3), oxamidate (4 and 5) or dithiooxamidate (6–8) ions. The heteronuclear nature of compounds 2 and 7 was additionally confirmed by high-resolution mass spectrometry. The magnetic properties of the Co2+ complexes were modelled taking into account zero-field splitting of this ion, yielding D-values for Co2+ in the range −17(1) to −50(1) cm−1. All the metal ion pairs in compounds 1–8 are antiferromagnetically-coupled, with J values between −10.0(1) and −45.0(2) cm−1 (via the exchange Hamiltonian Ĥex. = −2JŜ1Ŝ2) and |J| increasing in the order oxalate < oxamidate < dithiooxamidate. This tendency can be attributed to greater M–S bond covalency compared to M–N or M–O bonds (M = Co2+ and Ni2+). It was found that this antiferromagnetic coupling of Co2+ and Ni2+ ions through oxalate is more efficient for these tris(pyrazolyl)borate complexes than for similar oxalate-bridged systems with neutral aliphatic amine ligands.